JP2021172671A - Powdery fine cellulose fiber, resin composition, molding and method for producing the same - Google Patents
Powdery fine cellulose fiber, resin composition, molding and method for producing the same Download PDFInfo
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- JP2021172671A JP2021172671A JP2020074345A JP2020074345A JP2021172671A JP 2021172671 A JP2021172671 A JP 2021172671A JP 2020074345 A JP2020074345 A JP 2020074345A JP 2020074345 A JP2020074345 A JP 2020074345A JP 2021172671 A JP2021172671 A JP 2021172671A
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- fine cellulose
- resin
- cellulose fibers
- cellulose fiber
- fiber
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- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 139
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000011342 resin composition Substances 0.000 title claims description 30
- 238000000465 moulding Methods 0.000 title abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000011347 resin Substances 0.000 claims abstract description 72
- 239000000835 fiber Substances 0.000 claims abstract description 34
- 229920002678 cellulose Polymers 0.000 claims abstract description 28
- 239000001913 cellulose Substances 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- 238000004108 freeze drying Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000002612 dispersion medium Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001450 anions Chemical group 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000002121 nanofiber Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 description 36
- 238000004898 kneading Methods 0.000 description 25
- 238000007385 chemical modification Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 229920001131 Pulp (paper) Polymers 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
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- 238000001035 drying Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 238000010009 beating Methods 0.000 description 5
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JJXWHZXRUMIBNO-UHFFFAOYSA-N 4-[dimethoxy(methyl)silyl]oxybutan-1-amine Chemical compound CO[Si](C)(OC)OCCCCN JJXWHZXRUMIBNO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
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- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
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- 239000004677 Nylon Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
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- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
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- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
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- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- ICRFXIKCXYDMJD-UHFFFAOYSA-N n'-benzyl-n'-ethenyl-n-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN(C=C)CC1=CC=CC=C1 ICRFXIKCXYDMJD-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、樹脂中への分散性が良好な粉末状微細セルロース繊維、およびその製造方法に関する。 The present invention relates to a powdered fine cellulose fiber having good dispersibility in a resin and a method for producing the same.
ミクロフィブリル化セルロースやセルロースナノファイバーと呼ばれる微細セルロース繊維は軽量でありながら高弾性率・高強度という特徴から、近年、樹脂の強度や機能性を向上させる目的で微細セルロース繊維と複合化する開発がなされている。また、カーボンニュートラルであることやマイクロプラスチックによる海洋汚染の社会問題から脱プラスチックの動きが盛んになっており、植物由来の材料という点でも注目されている。この樹脂との複合化において、微細セルロース繊維は親水性が極めて高く、汎用の樹脂材料である疎水性のポリプロピレンやポリエチレンなどには特に分散性が悪いという問題がある。 Microfibrillated cellulose and fine cellulose fibers called cellulose nanofibers are lightweight yet have high elasticity and high strength. Therefore, in recent years, development has been developed to combine them with fine cellulose fibers for the purpose of improving the strength and functionality of the resin. It has been done. In addition, due to the fact that it is carbon-neutral and the social problem of marine pollution caused by microplastics, the movement to remove plastics is becoming active, and it is also attracting attention as a plant-derived material. In the compounding with this resin, the fine cellulose fiber has extremely high hydrophilicity, and there is a problem that the dispersibility is particularly poor in hydrophobic polypropylene, polyethylene, etc., which are general-purpose resin materials.
そこで、特許文献１では、木材パルプをアセチル化したのち、樹脂との混錬と同時にパルプの解繊を進行させることで、アセチル化微細セルロース繊維が均一に分散した樹脂を得る手法が提案されている。アセチル化はセルロースの耐熱性向上にも寄与し、また解繊工程と混錬を同時に行うため、低コストで製造できるという効果があるものの、得られる材料は必ず樹脂と複合化した樹脂組成物の形である。そのため、様々な樹脂、用途への応用を考えた場合、樹脂組成物の形態ではなく微細セルロース繊維単独の形態のみである方が応用への自由度が高いのは明白である。また、解繊が進行していない状態でアセチル化するため、解繊後にはアセチル化されてない微細セルロース繊維も含まれるため、微細セルロース繊維との複合化による効果が十分に発揮できていない恐れがある。 Therefore, Patent Document 1 proposes a method of obtaining a resin in which acetylated fine cellulose fibers are uniformly dispersed by acetylating wood pulp and then proceeding with defibration of the pulp at the same time as kneading with the resin. There is. Acetylation also contributes to improving the heat resistance of cellulose, and since the defibration process and kneading are performed at the same time, it has the effect of being able to be manufactured at low cost, but the obtained material is always a resin composition compounded with resin. It is a shape. Therefore, when considering application to various resins and applications, it is clear that the degree of freedom in application is higher when only the form of the fine cellulose fiber alone is used instead of the form of the resin composition. In addition, since acetylation occurs in a state where defibration has not progressed, fine cellulose fibers that have not been acetylated after defibration are also included, so there is a risk that the effect of compounding with fine cellulose fibers may not be fully exhibited. There is.
一方、特許文献２では、セルロースナノファイバーのスラリーに予め分散剤を添加し、凍結乾燥を経てナノファイバーを粉体化する方法および粉体化させたナノファイバーと樹脂とを混練させた組成物が提案されている。しかしながら、この手法では樹脂中のセルロースナノファイバーの分散性が向上するものの、分散剤とセルロースナノファイバーが結合していないため、分散剤がブリードアウトしてしまい、例えば混練後の樹脂組成物を利用する場面で他部材との接着性や密着性に不具合が生じる恐れがある。また、その分散剤が酸型の場合、樹脂組成物に含まれるセルロースナノファイバーの耐熱性が悪くなる。さらに、分散剤の対イオンが金属イオンの場合、セルロースナノファイバーが黄変したり、樹脂組成物を劣化させたり、樹脂組成物をプリント基板等の電子・電気部品に利用すると配線を腐食する恐れがある。 On the other hand, in Patent Document 2, a method in which a dispersant is added to a slurry of cellulose nanofibers in advance and freeze-dried to powder the nanofibers, and a composition in which the powdered nanofibers and a resin are kneaded are described. Proposed. However, although this method improves the dispersibility of the cellulose nanofibers in the resin, the dispersant bleeds out because the dispersant and the cellulose nanofibers are not bonded. For example, the resin composition after kneading is used. There is a risk that problems will occur in the adhesiveness and adhesion with other members. Further, when the dispersant is an acid type, the heat resistance of the cellulose nanofibers contained in the resin composition deteriorates. Furthermore, when the counterion of the dispersant is a metal ion, the cellulose nanofibers may turn yellow, the resin composition may be deteriorated, or the wiring may be corroded if the resin composition is used for electronic / electrical parts such as printed circuit boards. There is.
本発明は上述の状況を鑑みて為されたものであり、樹脂と複合化させた際に樹脂中での分散性が良好な微細セルロース繊維を単独の形態で得ることを課題とする。また、化学修飾された微細セルロース繊維と樹脂からなる組成物を成形する際の生産効率や他部材との接着性や密着性に優れた粉末状微細セルロース繊維を提供すること、および、当該微細セルロース繊維を容易に化学修飾することを可能とする製造方法を提供することにある。 The present invention has been made in view of the above circumstances, and an object of the present invention is to obtain a fine cellulose fiber having good dispersibility in a resin when it is combined with a resin in a single form. Further, it is possible to provide powdered fine cellulose fibers having excellent production efficiency when molding a composition composed of chemically modified fine cellulose fibers and a resin, and adhesiveness and adhesion to other members, and to provide the fine cellulose fibers. It is an object of the present invention to provide a manufacturing method capable of easily chemically modifying a fiber.
本発明者は上記課題を解決するために鋭意検討した結果、嵩密度が１０〜８５ｇ／Lである化学修飾された粉末状微細セルロース繊維とし、これを用いることで、分散剤を用いずとも樹脂中への分散性と樹脂成型時の生産性を両立できることを見出し、本発明を完成させた。 As a result of diligent studies to solve the above problems, the present inventor has obtained chemically modified fine cellulose fibers having a bulk density of 10 to 85 g / L, and by using this, a resin without using a dispersant. The present invention has been completed by finding that both dispersibility in the inside and productivity at the time of resin molding can be achieved at the same time.
すなわち、本発明は、嵩密度が１０〜８５ｇ／Ｌであり、化学修飾されていることを特徴とする粉末状微細セルロース繊維に関する。 That is, the present invention relates to a powdery fine cellulose fiber having a bulk density of 10 to 85 g / L and being chemically modified.
前記粉末状微細セルロース繊維の平均繊維径は３〜１０００ｎｍであることが好ましい。 The average fiber diameter of the powdered fine cellulose fibers is preferably 3 to 1000 nm.
前記粉末状微細セルロース繊維には分散剤を含まないことが好ましい。また、分散剤は陰イオン分散剤を含まないことがより好ましい。 It is preferable that the powdered fine cellulose fiber does not contain a dispersant. Further, it is more preferable that the dispersant does not contain an anion dispersant.
前記粉末状微細セルロース繊維には特に対イオンが金属イオンである分散剤を含まないことが好ましい。 It is particularly preferable that the powdered fine cellulose fiber does not contain a dispersant whose counterion is a metal ion.
また、本発明は、前記粉末状微細セルロース繊維及び樹脂を含む、樹脂組成物に関する。 The present invention also relates to a resin composition containing the powdered fine cellulose fibers and a resin.
さらに、本発明は、前記樹脂組成物を含む成形体に関する。 Furthermore, the present invention relates to a molded product containing the resin composition.
よりさらに、本発明は、微細セルロース繊維のペーストを凍結乾燥する工程と粉砕する工程とを有し、前記ペーストの固形分濃度が５．１〜９．０質量％未満である、粉末状微細セルロース繊維の製造方法にも関する。 Furthermore, the present invention comprises a step of freeze-drying and a step of pulverizing a fine cellulose fiber paste, and the solid content concentration of the paste is less than 5.1 to 9.0% by mass. It is also related to the method of manufacturing fibers.
前記ペーストの分散媒は水と有機溶媒の混合物であることが好ましい。 The dispersion medium of the paste is preferably a mixture of water and an organic solvent.
前記有機溶媒がアルコール類、カーボネート類のうち、少なくとも1種を含むことが好ましい。 The organic solvent preferably contains at least one of alcohols and carbonates.
前記ペーストにセルロースの化学修飾成分を含むことが好ましい。 It is preferable that the paste contains a chemically modified component of cellulose.
前記凍結乾燥する工程の後にセルロースを化学修飾する工程を有することが好ましい。 It is preferable to have a step of chemically modifying cellulose after the step of freeze-drying.
前記製造方法で得られる粉末状微細セルロース繊維の嵩密度は１０〜８５ｇ／Ｌであることが好ましい。 The bulk density of the powdered fine cellulose fibers obtained by the above production method is preferably 10 to 85 g / L.
本発明では、十分に化学修飾された粉末状微細セルロース繊維が得られることから、樹脂に対して均一に分散することができ、また混錬時の粘度が低いことから樹脂の成型性や生産効率にも優れ、さらに微細セルロース繊維が単独で得られるため、多様な種類の樹脂と複合させた樹脂組成物を様々な用途に使用することができる。 In the present invention, since a sufficiently chemically modified powdery fine cellulose fiber can be obtained, it can be uniformly dispersed in the resin, and since the viscosity at the time of kneading is low, the moldability and production efficiency of the resin can be obtained. Further, since fine cellulose fibers can be obtained alone, a resin composition compounded with various types of resins can be used for various purposes.
［粉末状微細セルロース繊維］
本発明の第１の態様は、嵩密度が１０〜８５ｇ／Ｌであり、化学修飾されていることを特徴とする粉末状微細セルロース繊維である。
[Powdered fine cellulose fiber]
The first aspect of the present invention is a powdery fine cellulose fiber having a bulk density of 10 to 85 g / L and being chemically modified.
粉末状微細セルロース繊維の嵩密度は１０〜８５ｇ／Ｌである必要がある。嵩密度の値は、ＪＩＳ Ｋ７３６５に従って測定される。嵩密度が１０ｇ／Ｌ未満では粉末状微細セルロース繊維の比表面積が大きすぎるため、当該粉末状微細セルロース繊維を樹脂と混錬する際の粘度が著しく上昇し、混錬時にローターにかかるトルクが高くなる。この混錬トルクが高くなると、良好な分散状態を得るために投入されるエネルギーや時間を過分に要してしまい、生産効率が悪くコストがかかる。嵩密度が８５ｇ／Ｌを超えると混錬トルクの上昇は低く抑えることができるが、当該粉末状微細セルロース繊維の樹脂中への分散性が悪く大きな粒子として存在するおそれがある。また、樹脂との複合化の際に粉末状微細化セルロースにより期待される引張強度、弾性率、靭性といった強度物性の向上や耐熱性、低い線熱膨張率といった熱安定性の向上などの効果が乏しくなるおそれがある。 The bulk density of the powdered fine cellulose fibers needs to be 10 to 85 g / L. The bulk density value is measured according to JIS K7365. If the bulk density is less than 10 g / L, the specific surface area of the powdered fine cellulose fibers is too large, so that the viscosity when the powdered fine cellulose fibers are kneaded with the resin increases remarkably, and the torque applied to the rotor during kneading is high. Become. When this kneading torque becomes high, the energy and time input to obtain a good dispersed state are excessively required, resulting in poor production efficiency and high cost. When the bulk density exceeds 85 g / L, the increase in the kneading torque can be suppressed to a low level, but the powdery fine cellulose fibers may have poor dispersibility in the resin and may exist as large particles. In addition, there are effects such as improvement of strength physical properties such as tensile strength, elastic modulus and toughness expected by powdered finely divided cellulose when compounded with resin, and improvement of thermal stability such as heat resistance and low linear thermal expansion coefficient. It may be scarce.
粉末状微細セルロース繊維は化学修飾されている。ここでの「化学修飾」とは、微細セルロース繊維の水酸基のすべて、もしくは部分的に水酸基とは異なる官能基に置換する任意の処理を意味する。粉末状微細セルロース繊維は、混練等の樹脂との複合化の際に使用する樹脂に応じて適切な官能基があるため、置換する官能基は任意に設計することができ、例えば汎用樹脂として代表的であるポリプロピレンやポリエチレンには水酸基とアシル化やエステル化させてアルキル基、シリル基、フェニル基等の疎水性を付与する官能基で化学修飾することが好ましい。セルロースの水酸基とのアシル化、エステル化は当該技術分野で周知・慣用であり、また微細セルロース繊維が粉末、水分散体、有機溶媒分散体といった状態ごとに適用できる化学修飾方法が異なるため、使用する化学修飾材料は特に限定されるものではない。特に、化学修飾としては、疎水化剤を用いてセルロースの水酸基を疎水性基に置換することが好ましい。このような疎水化の処理としては、アシル化、エステル化、アルキル化、エーテル化、トシル化、エポキシ化等の任意の疎水化が挙げられる。 The powdered fine cellulose fibers are chemically modified. The term "chemical modification" as used herein means an arbitrary treatment for substituting all or part of the hydroxyl groups of the fine cellulose fiber with a functional group different from the hydroxyl groups. Since the powdered fine cellulose fiber has an appropriate functional group depending on the resin used for compounding with the resin such as kneading, the functional group to be substituted can be arbitrarily designed, and is represented as a general-purpose resin, for example. It is preferable that the target polypropylene or polyethylene is chemically modified with a functional group that imparts hydrophobicity such as an alkyl group, a silyl group, or a phenyl group by acylating or esterifying the hydroxyl group with a hydroxyl group. Acylation and esterification of cellulose with hydroxyl groups are well known and commonly used in the art, and are used because the chemical modification methods that can be applied to fine cellulose fibers differ depending on the state such as powder, aqueous dispersion, and organic solvent dispersion. The chemically modified material to be used is not particularly limited. In particular, as a chemical modification, it is preferable to replace the hydroxyl group of cellulose with a hydrophobic group using a hydrophobic agent. Examples of such hydrophobization treatment include any hydrophobization such as acylation, esterification, alkylation, etherification, tosylation, and epoxidation.
粉末状微細セルロース繊維の「粉末状」とは、固体状の形態を有する微細セルロースが細かく砕かれた状態をいう。微細セルロース繊維の一部が粉末状でなくてもよい。 "Powdered" of powdered fine cellulose fibers refers to a state in which fine cellulose having a solid form is finely crushed. Some of the fine cellulose fibers do not have to be in powder form.
本発明の微細セルロース繊維は、セルロース繊維を微細化処理して得られる。セルロース繊維を微細化処理する装置は特に限定されるものではないが、例えば、高圧ホモジナイザー処理（マントン・ゴーリン型分散機による高圧分散処理）、ラニエタイプ圧力式ホモジナイザー、超高圧ホモジナイザー処理(アルテマイザーＴＭ（スギノマシン株式会社製））、ビーズミルや流星ミル等の分散装置、マスコロイダー（増幸産業株式会社製）等のホモジナイザー等が挙げられる。また、叩解度は特に限定しないが、微細化処理する前にダブルディスクリファイナー、ビーター等製紙用で使用している叩解機を前処理に使用することも可能である。特に高圧ホモジナイザーなどのオリフィスを通すタイプの微細化処理装置の場合、前処理で叩解をしないと原料が詰まったり、安定した微細化処理ができなくなる恐れがある。また、前記微細化処理装置は、一般的に生産効率が低いため、叩解機であらかじめ前処理を施した方が生産効率が高くなるため好ましい。さらに、ＴＥＭＰＯ酸化触媒を用いる化学処理によってナノファイバー化されたセルロースナノファイバー（ＴＯＣＮ）を用いることも可能ではあるが、叩解機で前処理を行い、ホモジナイザーで微細化する機械処理が好ましい。 The fine cellulose fiber of the present invention is obtained by refining the cellulose fiber. The apparatus for micronizing the cellulose fiber is not particularly limited, and for example, high-pressure homogenizer treatment (high-pressure dispersion treatment by a Manton-Gorlin type disperser), lanier type pressure homogenizer, and ultra-high pressure homogenizer treatment (ultemizer TM). (Manufactured by Sugino Machine Limited)), dispersers such as bead mills and meteor mills, homogenizers such as mass colloiders (manufactured by Masuyuki Sangyo Co., Ltd.), and the like. Further, the degree of beating is not particularly limited, but it is also possible to use a beating machine used for papermaking such as a double disc refiner and a beater for the preprocessing before the miniaturization processing. In particular, in the case of a miniaturization processing device of the type through which an orifice is passed, such as a high-pressure homogenizer, there is a risk that the raw material will be clogged or stable miniaturization processing will not be possible unless beating is performed in the pretreatment. Further, since the production efficiency of the miniaturization processing apparatus is generally low, it is preferable to perform pretreatment with a beating machine in advance because the production efficiency is high. Further, although it is possible to use cellulose nanofibers (TOCN) that have been nanofibered by chemical treatment using a TEMPO oxidation catalyst, mechanical treatment in which pretreatment is performed with a beating machine and finening is performed with a homogenizer is preferable.
微細化処理にあたり、使用可能なセルロース繊維は、特に限定はなく公知のものが使用でき、例えば、針葉樹晒クラフトパルプ（ＮＢＫＰ）、広葉樹晒クラフトパルプ（ＬＢＫＰ）、針葉樹晒サルファイトパルプ（ＮＢＳＰ）等の木材漂白化学パルプ、砕木パルプ（ＧＰ）、サーモメカニカルパルプ（ＴＭＰ）、ケミカルサーモメカニカルパルプ（ＢＣＴＭＰ）等の機械パルプ；麻、竹、藁、ケナフ、三椏、楮、木綿等の非木材パルプ；古紙パルプが使用できる。これらのセルロース繊維の１種を単独で又は２種以上を組み合わせて用いることができる。本発明では、特にセルロースＩ型、セルロースＩＩ型等のセルロースの型は限定されないが、好ましくはコットン、コットンリンター、木材パルプに代表されるような、セルロースＩ型の天然繊維である。さらに好ましくは、繊維の解繊時に切断よりもフィブリル化が進行しやすい針葉樹由来の漂白木材パルプのＮＢＫＰである。再生セルロースに代表されるセルロースＩＩ型の繊維はセルロースＩ型の繊維に比べ結晶化度が低くフィブリル化処理を行う際に、短繊維化しやすく、樹脂と複合化した際の強度向上の効果が低くなるおそれがあるため好ましくない。 The cellulose fibers that can be used in the micronization treatment are not particularly limited, and known ones can be used. Wood bleached chemical pulp, crushed wood pulp (GP), thermomechanical pulp (TMP), chemical thermomechanical pulp (BCTMP) and other mechanical pulp; hemp, bamboo, straw, kenaf, sansho, 楮, cotton and other non-wood pulp; Waste paper pulp can be used. One of these cellulose fibers can be used alone or in combination of two or more. In the present invention, the type of cellulose such as cellulose type I and cellulose type II is not particularly limited, but it is preferably a cellulose type I natural fiber such as cotton, cotton linter, and wood pulp. More preferably, it is NBKP of softwood-derived bleached wood pulp, which is more likely to be fibrillated than cut when the fibers are defibrated. Cellulose type II fibers typified by regenerated cellulose have a lower crystallinity than cellulose type I fibers, and tend to be shortened when fibrillated, and the effect of improving strength when combined with resin is low. It is not preferable because there is a risk of becoming.
前記セルロース繊維を主体とするが、必要に応じてこれにカチオン化パルプ、マーセル化パルプ等の変性パルプ、レーヨン、ビニロン、ナイロン、アクリル、ポリエステル、ポリオレフィン、カーボン、アラミド等の合成繊維や化学繊維、またはミクロフィブリル化パルプを単独で、あるいは混合して併用することができる。 Mainly the above-mentioned cellulose fiber, but if necessary, modified pulp such as cationized pulp and marcelified pulp, synthetic fiber and chemical fiber such as rayon, vinylon, nylon, acrylic, polyester, polyolefin, carbon and aramid, etc. Alternatively, microfibrillated pulp can be used alone or in combination.
セルロース繊維はセルロース分子の持つ水酸基により、水に均一に分散することが可能であるが、そのスラリーの粘度は、セルロース繊維の繊維長と表面積に依存する。セルロース繊維が細くなることは、それだけセルロースの表面積が増えるため、スラリーの粘度も必然的に上昇することになる。ＴＯＣＮなどの化学処理によって得られる微細セルロース繊維はシングルナノオーダーの繊維径で得られるが、上記の理由から極めて粘度が高いため濃度を高くすることができない。粉末状の化学修飾微細セルロース繊維を得る本発明においては、濃度はコストに大きく影響を受けるため、好ましくない。 Cellulose fibers can be uniformly dispersed in water due to the hydroxyl groups of cellulose molecules, but the viscosity of the slurry depends on the fiber length and surface area of the cellulose fibers. As the cellulose fibers become thinner, the surface area of the cellulose increases, and the viscosity of the slurry inevitably increases. Fine cellulose fibers obtained by chemical treatment such as TOCN can be obtained with a fiber diameter on the order of single nano, but the concentration cannot be increased due to the extremely high viscosity for the above reasons. In the present invention for obtaining powdered chemically modified fine cellulose fibers, the concentration is greatly affected by the cost, which is not preferable.
本発明における、化学修飾された微細セルロース繊維の平均繊維径は３ｎｍ〜１０００ｎｍであることが好ましく、より好ましくは３ｎｍ〜５００ｎｍ、さらに好ましくは３ｎｍ〜３００ｎｍ、よりさらに好ましくは３ｎｍ〜２００ｎｍ、最も好ましくは３０ｎｍ〜２００ｎｍである。繊維径がこの範囲であることで樹脂と混錬した際の分散性が良好となり、後述するような、微細セルロース繊維により期待される種々の効果が発現する。平均繊維径の測定は以下の手順で行う。まず、化学修飾された繊維セルロース繊維の粉末を試料台に載せ、高分解能電子顕微鏡（ＦＥ−ＳＥＭ）で観察し、得られたＳＥＭ画像の水平方向、および垂直方向にラインを引く。次に、二つのラインで交差するすべての繊維の繊維径を拡大画像から実測し、測定結果から数平均繊維径を算出する。さらに、試料台に載せた粉末の表面の少なくとも２箇所について同様に数平均繊維径を算出し、全ての数平均繊維径の平均値を平均繊維径とする。 The average fiber diameter of the chemically modified fine cellulose fibers in the present invention is preferably 3 nm to 1000 nm, more preferably 3 nm to 500 nm, still more preferably 3 nm to 300 nm, still more preferably 3 nm to 200 nm, and most preferably. It is 30 nm to 200 nm. When the fiber diameter is in this range, the dispersibility when kneaded with the resin is improved, and various effects expected from the fine cellulose fibers, which will be described later, are exhibited. The average fiber diameter is measured by the following procedure. First, the chemically modified fiber cellulose fiber powder is placed on a sample table, observed with a high-resolution electron microscope (FE-SEM), and lines are drawn in the horizontal direction and the vertical direction of the obtained SEM image. Next, the fiber diameters of all the fibers intersecting at the two lines are measured from the enlarged image, and the number average fiber diameter is calculated from the measurement results. Further, the number average fiber diameter is calculated in the same manner for at least two places on the surface of the powder placed on the sample table, and the average value of all the number average fiber diameters is used as the average fiber diameter.
セルロース繊維はその水酸基により、脱水工程において繊維同士が水素結合を行う性質を持っている。この水素結合形成の工程において例えば紙などのシートの場合は強度が発現する一方で、繊維間が相互作用により乾燥工程における収縮が生じる。特に繊維径が細くなるに従い繊維の剛度が下がり、また繊維間に働く凝集力が大きくなるため、この収縮が顕著に見られる。また極度にフィブリル化が進んだ繊維を用いて作成したシートは繊維間が完全に密着するために作成したフィルムは透明化することが知られている。つまり、通常の脱水や乾燥方法では微細セルロース繊維を単離することは困難である。このため、微細セルロース繊維を単離するには乾燥時の収縮を抑えること、または繊維間の水素結合を阻害させることが必要となる。これまでに提案されている具体的な手法は、微細セルロース繊維をアセトンのような親水性の溶媒に置換した後、更にトルエンとアセトンの混合溶媒といったより疎水性の高い溶媒に置換して乾燥させる等の方法が提案されている。しかしながら、この手法は２つの問題点がある。まず一つは分散溶媒の水からアセトンに溶媒置換する作業である。セルロース繊維は、繊維径が細くなるに従い保水性が高くなるため、水から溶媒への置換は非常に時間のかかる作業となっており実生産の面で生産性を下げる要因となっている。また、疎水性の高い溶媒で置換されているため、水素結合は阻害されており、溶媒の表面張力も低いため、凝集力も水に比べれば小さくなるものの、収縮は生じるため、微細セルロース繊維が本来有していた大きな比表面積の低下は免れない。 Cellulose fibers have the property of forming hydrogen bonds between fibers in the dehydration process due to their hydroxyl groups. In the process of forming hydrogen bonds, for example, in the case of a sheet such as paper, strength is developed, but shrinkage occurs in the drying process due to the interaction between the fibers. In particular, as the fiber diameter becomes smaller, the rigidity of the fiber decreases, and the cohesive force acting between the fibers increases, so that this shrinkage is remarkable. Further, it is known that a sheet made of fibers having extremely advanced fibrillation is made transparent because the fibers are completely adhered to each other. That is, it is difficult to isolate fine cellulose fibers by a normal dehydration or drying method. Therefore, in order to isolate fine cellulose fibers, it is necessary to suppress shrinkage during drying or to inhibit hydrogen bonds between the fibers. The specific method proposed so far is to replace the fine cellulose fibers with a hydrophilic solvent such as acetone, and then further replace the fine cellulose fibers with a more hydrophobic solvent such as a mixed solvent of toluene and acetone and dry the fibers. Etc. have been proposed. However, this method has two problems. The first is the work of substituting acetone for the dispersion solvent water. Since the water retention of cellulose fibers increases as the fiber diameter becomes smaller, the replacement of water with a solvent is a very time-consuming operation, which is a factor that lowers the productivity in terms of actual production. In addition, since it is replaced with a highly hydrophobic solvent, hydrogen bonds are inhibited, and the surface tension of the solvent is low, so that the cohesive force is smaller than that of water, but shrinkage occurs, so that the fine cellulose fibers are originally It is inevitable that the specific surface area will be greatly reduced.
そこで、微細化処理後の微細セルロース繊維を収縮、および凝集することなく水を除去するために凍結乾燥することが好ましい。凍結乾燥とは、セルロース繊維と分散媒の混合物を凍結状態のまま減圧して分散媒を昇華させることによって材料を収縮させることなく乾燥することができる手法である。本発明では、前記微細化処理後の微細セルロース繊維と分散媒からなるペーストを凍結乾燥することが好ましい。凍結乾燥におけるペーストの凍結方法は特に限定されないが、例えば、液体窒素などの冷媒の中にペーストを入れて凍結させる方法、大気圧化でペーストを低温雰囲気に置いて凍結させる方法、減圧下でペーストを低温雰囲気下に置いて凍結させる方法がある。好ましくは、大気圧下でペーストを低温雰囲気に置いて凍結させる方法である。ペーストの凍結温度は、分散媒の凝固点以下にする必要があり、−２０℃以下が好ましく、−３０℃以下であることがより好ましい。凍結乾燥は凍結後に昇華させるが、減圧下でなければ乾燥が遅くなる。減圧時の圧力は０．１０ｋＰａ以下が好ましく、０．０５ｋＰａ以下がより好ましい。 Therefore, it is preferable to freeze-dry the fine cellulose fibers after the micronization treatment in order to remove water without shrinking and agglutinating. Freeze-drying is a method in which a mixture of cellulose fibers and a dispersion medium is decompressed in a frozen state to sublimate the dispersion medium so that the material can be dried without shrinking. In the present invention, it is preferable to freeze-dry the paste composed of the fine cellulose fibers and the dispersion medium after the micronization treatment. The method of freezing the paste in freeze-drying is not particularly limited, but for example, a method of putting the paste in a refrigerant such as liquid nitrogen and freezing it, a method of freezing the paste in a low temperature atmosphere at atmospheric pressure, and a method of freezing the paste under reduced pressure. There is a method of freezing the paste in a low temperature atmosphere. A method of freezing the paste in a low temperature atmosphere under atmospheric pressure is preferable. The freezing temperature of the paste needs to be equal to or lower than the freezing point of the dispersion medium, preferably −20 ° C. or lower, and more preferably −30 ° C. or lower. Freeze-drying sublimates after freezing, but drying is slow unless it is under reduced pressure. The pressure at the time of depressurization is preferably 0.10 kPa or less, more preferably 0.05 kPa or less.
本発明において、前記微細セルロース繊維のペーストに用いる分散媒は、水と有機溶媒の混合物とすることが好ましく、有機溶媒としてアルコール類、カーボネート類のうち少なくとも一種を含む混合ペーストとすることがより好ましい。このような有機溶媒を混合させることで、乾燥時の微細セルロース繊維の凝集を抑制することができる。アルコール類およびカーボネート類としては、水と均一に混和できれば特に限定はされないが、昇華した有機溶媒を凍結することで回収できるｔ−ブチルアルコール、およびエチレンカーボネートが特に好ましい。分散溶媒中の前記有機溶媒の含有量は、１０％以上が好ましく、さらに好ましくは２０％以上である。 In the present invention, the dispersion medium used for the fine cellulose fiber paste is preferably a mixture of water and an organic solvent, and more preferably a mixed paste containing at least one of alcohols and carbonates as the organic solvent. .. By mixing such an organic solvent, aggregation of fine cellulose fibers during drying can be suppressed. The alcohols and carbonates are not particularly limited as long as they can be uniformly miscible with water, but t-butyl alcohol and ethylene carbonate, which can be recovered by freezing the sublimated organic solvent, are particularly preferable. The content of the organic solvent in the dispersion solvent is preferably 10% or more, more preferably 20% or more.
本発明において、前記混合ペースト中の微細セルロース繊維の濃度は５．１％以上９．０％未満であることが好ましい。混合ペースト中の微細セルロース繊維が５．１％未満の場合、混合ペーストの分散媒中での微細セルロース繊維の分散性は良好だが、凍結乾燥後に高い比表面積となるため、樹脂と混錬する際の粘度が高くなり、樹脂組成物を成形する際の作業効率、生産効率が悪くなり、実用性に欠けるため好ましくない。さらに、その高い比表面積のため、化学修飾する際に部分的に修飾されない繊維が増えることにより、樹脂中で分散しない凝集物を発生させてしまうおそれがある。また、混合ペースト中の微細セルロース繊維が９．０％以上になると、後工程の粉砕工程や樹脂との混錬工程でも粉砕・分散しきれない微細セルロース繊維の凝集物が多くなり、樹脂と複合化した際の微細セルロース繊維の分散性が悪くなり、樹脂の透明度の低下や強度向上効果が得難いため好ましくない。 In the present invention, the concentration of the fine cellulose fibers in the mixed paste is preferably 5.1% or more and less than 9.0%. When the fine cellulose fibers in the mixed paste are less than 5.1%, the dispersibility of the fine cellulose fibers in the dispersion medium of the mixed paste is good, but the specific surface area becomes high after freeze-drying, so that when kneading with the resin It is not preferable because the viscosity of the resin composition becomes high, the work efficiency and production efficiency at the time of molding the resin composition deteriorate, and the practicality is lacking. Further, due to its high specific surface area, the number of fibers that are not partially modified during chemical modification increases, which may cause agglomerates that are not dispersed in the resin. Further, when the content of the fine cellulose fibers in the mixed paste is 9.0% or more, the agglomerates of the fine cellulose fibers that cannot be completely crushed and dispersed even in the crushing step in the subsequent step or the kneading step with the resin increase, and are composited with the resin. It is not preferable because the dispersibility of the fine cellulose fibers at the time of conversion is deteriorated, and it is difficult to obtain the effect of lowering the transparency of the resin and improving the strength.
微細セルロース繊維の凍結乾燥後の乾燥物を粉末状にするにあたっては、粉砕する工程を必要とする。粉砕する工程で使用する粉砕機としては、カッターミル、ボールミル、ディスクミル、気流式粉砕機などが挙げられ、その中で凍結乾燥後の微細セルロース繊維を塊状に凝集させない条件設定ができる装置であれば特に限定されないが、カッターミルでプレ粉砕したのち、気流式粉砕機を用いることが好ましい。気流式粉砕機は、原料同士を衝突させる衝撃で粉砕するため、原料に必要以上の圧縮力がかからず、粉末の嵩密度を低くすることができるため好ましい。気流式粉砕機としては、例えば、スーパージェットミル（日清エンジニアリング株式会社製）やドライバースト（スギノマシン株式会社製）等が挙げられる。 A step of pulverizing the dried product after freeze-drying of the fine cellulose fibers is required. Examples of the crusher used in the crushing process include a cutter mill, a ball mill, a disc mill, and an air flow type crusher, and any device that can set conditions that do not agglomerate fine cellulose fibers after freeze-drying into a lump. The present invention is not particularly limited, but it is preferable to use an air flow type crusher after pre-grinding with a cutter mill. Since the airflow type crusher crushes the raw materials by the impact of colliding with each other, the raw materials are not subjected to an unnecessarily compressive force, and the bulk density of the powder can be lowered, which is preferable. Examples of the airflow type crusher include a super jet mill (manufactured by Nisshin Engineering Co., Ltd.) and a dry strike (manufactured by Sugino Machine Limited).
本発明では、凍結乾燥後の乾燥物である多孔質体の密度が０．０５１ｇ／ｃｍ３以上０．０９０ｇ／ｃｍ３未満であることが好ましい。多孔質体の密度が０．０５１ｇ／ｃｍ３未満の場合、微細セルロース繊維の比表面積が大きいため、粉砕後の嵩密度が低くなりすぎてしまい、樹脂組成物の生産効率に影響する樹脂トルクが上昇してしまうことや化学修飾工程セルロースの水酸基を十分に別の官能基に置換できないおそれがあるため好ましくない。また、０．０９０ｇ／ｃｍ３以上の場合は、粉砕後の嵩密度が低くなるため、樹脂トルクの上昇は抑制できるが、微細セルロース繊維を樹脂中に均一に分散することができなくなるため好ましくない。多孔質体の密度は、前記ペーストの濃度に依存するため、多孔質体の密度は前記ペーストの固形分濃度で調整することができる。 In the present invention, it is preferable that the density of the porous body which is a dried product after freeze-drying is 0.051 g / cm 3 or more and less than 0.090 g / cm 3. When the density of the porous body is less than 0.051 g / cm 3 , the specific surface area of the fine cellulose fibers is large, so that the bulk density after pulverization becomes too low, and the resin torque that affects the production efficiency of the resin composition is increased. It is not preferable because it may rise or the hydroxyl group of the chemical modification step cellulose may not be sufficiently replaced with another functional group. Further, in the case of 0.090 g / cm 3 or more, the bulk density after pulverization becomes low, so that the increase in the resin torque can be suppressed, but it is not preferable because the fine cellulose fibers cannot be uniformly dispersed in the resin. .. Since the density of the porous body depends on the concentration of the paste, the density of the porous body can be adjusted by the solid content concentration of the paste.
粉末状微細セルロース繊維は化学修飾されている。化学修飾する工程は凍結乾燥する工程と同時に行ってもよく、凍結乾燥工程の後でも構わない。凍結乾燥する工程と同時に行う微細セルロース繊維の化学修飾方法は、混合ペースト中の水の存在下で微細セルロース繊維を処理することができ、樹脂と混錬する際に分散性が良好で混錬時の粘度が著しく向上しない限りは特に限定されないが、例えばシランカップリング剤が好適に用いられる。シランカップリング剤は、ビニル基、エポキシ基、メタクリル基、フェニル基、アミノ基、フルオロ基、イソシアネート基など様々な官能基を有する化合物が工業的に製造されており、化学修飾の設計の幅が広い。そのため、複合化する樹脂に合わせて化学修飾微細セルロース繊維の設計することができるため好ましい。シランカップリング剤としては、例えば、トリメトキシフェニルシラン、フェニルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３,４−エポキシシクロヘキシル）エチルトリメトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルメチルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビニルトリメトキシシラン、Ｎ−（２−（ビニルベンジルアミノ）エチル）３−アミノプロピルトリメトキシシラン塩酸塩、３−メタクリロキシプロピルトリメトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルトリメトキシシラン等が挙げられる。また、イソシアネート化合物もシランカップリング剤と同様に様々な官能基を有する化合物が工業的に製造されており、化学修飾の幅が広く、安価な材料であるため、コスト面でも優れている。ただし、イソシアネート基は水酸基との反応性が非常に高いため、凍結乾燥工程中で化学修飾する場合は、イソシアネート基をブロック化しているトリレンジイソシアネート（TDI）やジフェニルメタンジイソシアネート（MDI）などが好ましい。化学修飾工程を凍結乾燥工程と同時に実施することは工程を削減することができるため、低コストであるというメリットがあるが、混合ペーストには水が含まれているため、水との反応性が高い試薬を用いての修飾や低極性の溶媒中で反応させる手法をとることができないというデメリットがある。 The powdered fine cellulose fibers are chemically modified. The step of chemically modifying may be performed at the same time as the step of freeze-drying, or may be performed after the step of freeze-drying. The chemical modification method of the fine cellulose fibers performed at the same time as the freeze-drying step can treat the fine cellulose fibers in the presence of water in the mixed paste, and has good dispersibility when kneaded with the resin, and during kneading. Although not particularly limited as long as the viscosity of the above is not significantly improved, for example, a silane coupling agent is preferably used. As the silane coupling agent, compounds having various functional groups such as a vinyl group, an epoxy group, a methacryl group, a phenyl group, an amino group, a fluoro group, and an isocyanate group are industrially produced, and the range of chemical modification designs is wide. wide. Therefore, it is preferable because the chemically modified fine cellulose fiber can be designed according to the resin to be composited. Examples of the silane coupling agent include trimethoxyphenylsilane, phenyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) ) 3-Aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane Examples thereof include hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane and the like. Further, as for the isocyanate compound, a compound having various functional groups is industrially produced as in the case of the silane coupling agent, the range of chemical modification is wide, and the material is inexpensive, so that it is also excellent in terms of cost. However, since the isocyanate group has a very high reactivity with the hydroxyl group, toluene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI) in which the isocyanate group is blocked is preferable when chemically modifying the isocyanate group in the freeze-drying step. Performing the chemical modification step at the same time as the freeze-drying step has the advantage of low cost because the number of steps can be reduced, but since the mixed paste contains water, it is reactive with water. There is a demerit that it is not possible to modify with a high reagent or to react in a low-polarity solvent.
本発明では、凍結乾燥工程中で化学修飾を行わない場合、粉砕工程後に化学修飾工程を行う。凍結乾燥工程と粉末工程を経た微細セルロース繊維粉末であれば、トルエンやヘキサンなどの低極性溶媒中での化学修飾が可能となるが、樹脂と混錬する際に分散性が良好で混錬時の粘度が著しく向上しない限りはこれに限定されないが、水を含む反応は処理後に水を除去しない限り微細セルロース繊維粉末を再凝集させてしまうため好ましくない。
例えば、シランカップリング剤を使う場合は加水分解水溶液ではなく、シラン原液、もしくは有機溶媒の希釈液を用いるか蒸着などの気相法で化学修飾することが好ましい。また、イソシアネート化合物については凍結乾燥工程で水分を除去しているため、イソシアネート基をブロック化していないオクタデシルイソシアネート、フェニルイソシアネートなどを用いることができる。ブロック化していないイソシアネートは水酸基との反応性が極めて高いため、ブロック化したイソシアネートよりも低温で反応が進行するため好ましい。さらに、簡便な方法で製造コストも低く、化学修飾後でも高い耐熱性を維持できるアセチル化も好ましく用いることができる。
In the present invention, when the chemical modification is not performed in the freeze-drying step, the chemical modification step is performed after the pulverization step. Fine cellulose fiber powder that has undergone the freeze-drying process and the powder process can be chemically modified in a low-polarity solvent such as toluene or hexane, but it has good dispersibility when kneaded with a resin and is used during kneading. The reaction including water is not preferable as long as the viscosity of the above is not significantly improved, because the fine cellulose fiber powder is reaggregated unless water is removed after the treatment.
For example, when a silane coupling agent is used, it is preferable to use a silane stock solution, a diluted solution of an organic solvent, or chemically modify by a vapor phase method such as vapor deposition instead of a hydrolyzed aqueous solution. Further, since water is removed from the isocyanate compound in the freeze-drying step, octadecyl isocyanate or phenyl isocyanate in which the isocyanate group is not blocked can be used. Since unblocked isocyanate has extremely high reactivity with hydroxyl groups, the reaction proceeds at a lower temperature than blocked isocyanate, which is preferable. Further, acetylation, which is a simple method, has a low production cost, and can maintain high heat resistance even after chemical modification, can also be preferably used.
粉末状微細セルロース繊維は、分散剤を含まないことが好ましい。分散剤を含むと、粉末状微細セルロース繊維と樹脂とを混合して樹脂の組成物を形成する工程においては、樹脂中での粉末状微細セルロース繊維の分散性が向上し、樹脂組成物の力学的性能が向上するなどの効果が得られるが、得られた樹脂組成物を実際に使用する場面においては、他部材と組み合わせて、また接着、複合化させて使用することがある。このような場面では、他部材との接着性や密着性に不具合が生じるおそれがあるため好ましくない。ここでの分散剤とは、粉末状微細セルロース繊維を水に分散する際に分散性が向上するものであれば特に限定はなく、公知のものを指すが、特に、分散剤が陰イオン分散剤では対イオンの影響を受けて樹脂組成物に含まれる微細セルロース繊維に悪影響をおよぼす。例えば、対イオンがプロトンになるリン酸基、カルボン酸基、スルホン酸基などを構造にもつ分散剤の場合、ｐＨが酸性になるため、微細セルロース繊維の耐熱性や強度が劣化する。さらに、それら分散剤の対イオンが金属イオン、特にＮａなどのアルカリ金属の場合は、セルロースの加熱や経時での黄変を促進させるため、外観や意匠性の問題によりパソコン、スマートフォン、家電製品、玩具などの部材・筐体の用途に適さない。また、対イオンがアンモニウム塩の場合は、加熱時にアンモニアガスとして脱離することがある。具体的にはアンモニウム塩型のカルボキシメチルセルロースは１５０℃程度の加熱により、アンモニアが脱離して酸型になることが知られている。熱可塑性樹脂と混錬する場合、少なくとも２００℃程度の熱をかけるため、アンモニアが発生する条件に容易に達する。発生したアンモニアガスは、樹脂の劣化を促進する。例えば、航空機・自動車など輸送機器、電気・電子光学・医療機器、防弾ガラスの材料など幅広く使用されているポリカーボネートは、アンモニアにより加水分解して劣化することが知られている。また、分散剤には製造過程で除去しきれずに残留する塩素などのハロゲン系元素が不純物として含まれることがあり、これらハロゲン系元素はプリント基板などの電子・電気部品の配線を腐食するおそれがある。 The powdered fine cellulose fibers preferably do not contain a dispersant. When a dispersant is contained, in the step of mixing the powdered fine cellulose fibers and the resin to form a resin composition, the dispersibility of the powdered fine cellulose fibers in the resin is improved, and the dynamics of the resin composition is improved. Although effects such as improvement in performance can be obtained, in the actual use of the obtained resin composition, it may be used in combination with other members, or by bonding or compounding. In such a situation, it is not preferable because there is a possibility that problems may occur in the adhesiveness and adhesion to other members. The dispersant here is not particularly limited as long as it improves dispersibility when powdered fine cellulose fibers are dispersed in water, and refers to known ones. In particular, the dispersant is an anion dispersant. Then, it is affected by counterions and adversely affects the fine cellulose fibers contained in the resin composition. For example, in the case of a dispersant having a structure such as a phosphoric acid group, a carboxylic acid group, or a sulfonic acid group whose counterion becomes a proton, the pH becomes acidic, so that the heat resistance and strength of the fine cellulose fibers deteriorate. Furthermore, when the counterion of these dispersants is a metal ion, especially an alkali metal such as Na, heating of cellulose and yellowing over time are promoted. Not suitable for use in parts and housings such as toys. When the counterion is an ammonium salt, it may be desorbed as ammonia gas during heating. Specifically, it is known that ammonium salt-type carboxymethyl cellulose is desorbed from ammonia and becomes an acid type by heating at about 150 ° C. When kneading with a thermoplastic resin, heat of at least about 200 ° C. is applied, so that the conditions for generating ammonia can be easily reached. The generated ammonia gas accelerates the deterioration of the resin. For example, polycarbonate, which is widely used in transportation equipment such as aircraft and automobiles, electrical / electro-optical / medical equipment, and bulletproof glass materials, is known to be hydrolyzed and deteriorated by ammonia. In addition, the dispersant may contain halogen-based elements such as chlorine that cannot be completely removed during the manufacturing process as impurities, and these halogen-based elements may corrode the wiring of electronic and electrical parts such as printed circuit boards. be.
本発明の樹脂組成物には熱可塑性樹脂、熱硬化性樹脂、ゴムを用いることができる。使用できる樹脂の種類に特に制限はないが、熱可塑性樹脂の例としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ乳酸樹脂、ポリビニルアルコール樹脂、ポリアミド樹脂、アクリロニトリル− ブタジエン− スチレン（ＡＢＳ）樹脂、アクリロニトリル− スチレン（ＡＳ）樹脂、ポリメチルメタクリレート樹脂、ポリ塩化ビニリデン樹脂、エチレンビニルアルコール樹脂、ポリアクリロニトリル樹脂、ポリアセタール樹脂、ポリケトン樹脂、および環状ポリオレフィン樹脂が挙げられる。熱硬化性樹脂の例としては、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂などが挙げられる。ゴムの例としては天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、スチレン− ブタジエン共重合体ゴム（ＳＢＲ）、ポリブタジエンゴム（ＢＲ）、ブチルゴム（ＩＩＲ）、ニトリルゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、アクリルゴム（ＡＣＭ）、フッ素ゴム（ＦＫＭ）、エチレンプロピレンゴム（ＥＰＤＭ）、クロロスルホン化ポリエチレン（ＣＳＭ）、ウレタンゴム（Ｕ）、シリコーンゴム（Ｑ）など挙げられる。その他、本発明の性能を損なわない範囲で、樹脂組成物には消泡剤、防腐剤、充填剤、着色剤、可塑剤、レベリング剤、導電剤、帯電防止剤、紫外線吸収剤、消臭剤、耐熱材等の助剤等や強化繊維、導電繊維、耐熱繊維等の繊維材料を適宜混合することできる。 A thermoplastic resin, a thermosetting resin, and a rubber can be used for the resin composition of the present invention. The type of resin that can be used is not particularly limited, but examples of thermoplastic resins include polyethylene resin, polypropylene resin, polylactic acid resin, polyvinyl alcohol resin, polyamide resin, acrylonitrile-butadiene-styrene (ABS) resin, and acrylonitrile-styrene. Examples thereof include (AS) resin, polymethylmethacrylate resin, polyvinylidene chloride resin, ethylene vinyl alcohol resin, polyacrylonitrile resin, polyacetal resin, polyketone resin, and cyclic polyolefin resin. Examples of thermosetting resins include epoxy resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins and the like. Examples of rubber include natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), butyl rubber (IIR), nitrile rubber (NBR), and chloroprene rubber (CR). ), Acrylic rubber (ACM), Fluoro rubber (FKM), Ethylene propylene rubber (EPDM), Chlorosulfonated polyethylene (CSM), Urethane rubber (U), Silicone rubber (Q) and the like. In addition, as long as the performance of the present invention is not impaired, the resin composition includes a defoaming agent, a preservative, a filler, a coloring agent, a plasticizer, a leveling agent, a conductive agent, an antistatic agent, an ultraviolet absorber, and a deodorant. , Auxiliary agents such as heat-resistant materials and fiber materials such as reinforcing fibers, conductive fibers and heat-resistant fibers can be appropriately mixed.
本発明の樹脂組成物は、様々な成形方法で成形品として得ることができる。樹脂の種類や求める成形品の形によって適切な成形方法は適宜使い分ける必要があるが、例えば、押出成形、射出成形、熱プレス成形、溶融押出成形、ブロー成形、真空成型、加熱成形などが挙げられる。 The resin composition of the present invention can be obtained as a molded product by various molding methods. It is necessary to appropriately use an appropriate molding method depending on the type of resin and the shape of the desired molded product, and examples thereof include extrusion molding, injection molding, hot press molding, melt extrusion molding, blow molding, vacuum molding, and heat molding. ..
［樹脂組成物］
本発明の第２の態様は、前記の粉末状微細セルロース繊維及び樹脂を含む、樹脂組成物である。
[Resin composition]
A second aspect of the present invention is a resin composition containing the powdered fine cellulose fibers and the resin.
粉末状微細セルロース繊維、樹脂及び樹脂組成物は、本発明の第１の態様における上記説明が第２の態様にも当てはまる。 For the powdered fine cellulose fiber, the resin and the resin composition, the above description in the first aspect of the present invention also applies to the second aspect.
粉末状微細セルロース繊維及び樹脂を複合化させる手法としては特に限定はなく、溶融混練、乾式混合等の公知の手法が挙げられるが、溶融混練をすることが好ましい。混練にあたり、粉末状微細セルロース繊維が粉末状であることにより、樹脂と均一に分散することができる。また、樹脂の種類に応じた化学修飾を付与しておくことができる。混練には、押出機、ミキシングローラ、ニーダ、ミキサー等の公知の混練機を用いることができる。 The method for compounding the powdered fine cellulose fiber and the resin is not particularly limited, and known methods such as melt-kneading and dry-kneading can be mentioned, but melt-kneading is preferable. When kneading, the powdery fine cellulose fibers are in the form of powder, so that they can be uniformly dispersed with the resin. In addition, chemical modification according to the type of resin can be imparted. For kneading, a known kneader such as an extruder, a mixing roller, a kneader, or a mixer can be used.
［成形体］
本発明の第３の態様は、樹脂組成物を含有する成形体である。
[Molded product]
A third aspect of the present invention is a molded product containing a resin composition.
樹脂組成物は、本発明の第２の態様における上記説明が第３の態様にも当てはまる。 For the resin composition, the above description in the second aspect of the present invention also applies to the third aspect.
成形体とは、フィルム状、シート状、構造体等の任意の形態を指し、樹脂組成物を用いて作製される。成形体を作製する方法は特に限定はなく公知の手法が用いられ、例えば、射出成形、押出成形、ブロー成形、プレス成形等が適用できる。 The molded body refers to an arbitrary form such as a film shape, a sheet shape, a structure, etc., and is produced by using a resin composition. The method for producing the molded product is not particularly limited, and a known method is used. For example, injection molding, extrusion molding, blow molding, press molding and the like can be applied.
成形体は、使用目的に応じて、その形態や作製方法を選択できる。電子機器、家電製品、各種の容器、建材、家具、文具、自動車、家庭用品に使用されている部材に代えて用いることができる。例えば、電子機器や家電製品の筐体および外装部品、各種の収納ケース、食器類、建材のインテリア部材、自動車の内装材、その他の日常生活用品にも使用することができる。 The form and manufacturing method of the molded product can be selected according to the purpose of use. It can be used in place of materials used in electronic devices, home appliances, various containers, building materials, furniture, stationery, automobiles, and household goods. For example, it can be used for housings and exterior parts of electronic devices and home appliances, various storage cases, tableware, interior materials for building materials, interior materials for automobiles, and other daily necessities.
［粉末状微細セルロース繊維の製造方法］
本発明の第４の態様は、微細セルロース繊維のペーストを凍結乾燥する工程と粉砕する工程とを有し、前記ペーストの固形分濃度が５．１〜９．０質量％未満であることを特徴とする、粉末状微細セルロース繊維の製造方法である。
[Manufacturing method of powdered fine cellulose fiber]
A fourth aspect of the present invention comprises a step of freeze-drying a fine cellulose fiber paste and a step of pulverizing the paste, and the solid content concentration of the paste is less than 5.1 to 9.0% by mass. This is a method for producing powdered fine cellulose fibers.
微細セルロース繊維、ペースト、凍結乾燥、粉砕、粉末状微細セルロース繊維には、本発明の第１〜３の態様における上記説明が第４の態様にも当てはまる。 For fine cellulose fibers, pastes, freeze-dried, pulverized, and powdered fine cellulose fibers, the above description in the first to third aspects of the present invention also applies to the fourth aspect.
ペーストの固形分濃度を５．１質量％以上とすることで嵩密度は大きくなるものの、化学修飾されない微細セルロース繊維を少なくすることができ、樹脂との混錬時に分散不良が発生しにくくなる。また、固形分濃度を９．０質量％未満とすることで前記嵩密度を満たすことができる。 By setting the solid content concentration of the paste to 5.1% by mass or more, the bulk density is increased, but the number of fine cellulose fibers that are not chemically modified can be reduced, and dispersion defects are less likely to occur during kneading with the resin. Further, the bulk density can be satisfied by setting the solid content concentration to less than 9.0% by mass.
本発明の粉末状微細セルロース繊維の製造方法により、樹脂と混練等の複合化をする際に良好な分散性をもって樹脂の組成物を作製でき、さらに樹脂組成物が良好な成形性を発揮することができる。 According to the method for producing powdered fine cellulose fibers of the present invention, a resin composition can be produced with good dispersibility when compounded with a resin such as kneading, and the resin composition exhibits good moldability. Can be done.
以下、本発明を実施例及び比較例を用いてより具体的に説明するが、本発明の範囲は実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the Examples.
[実施例中の測定項目および試験方法]
（混錬試験）
混錬試験には混錬機（商品名：ラボプラストミル、型式：４Ｃ−１５０、株式会社東洋精機製）、ミキサー（型番：Ｒ６０、株式会社東洋精機製）を用いた。ポリプロピレン樹脂（型番：Ｊ１０５Ｇ、株式会社プライムポリマー製）を４１ｇ計量し、２２０℃に加熱したミキサーに投入し、１０ｒｐｍで予備混錬を行った。その後、３０ｒｐｍに回転数を変更し、微細セルロース繊維粉末を１ｇ計量して投入し、投入が完了したのちは５０ｒｐｍに回転数を変更し、１０分間混錬した。混錬終了時のトルク値を読み取り、以下の基準で〇以上を合格とした。
◎：樹脂のみのトルク値の１．２倍以下
〇：樹脂のみのトルク値の１．５倍以下
△：樹脂のみのトルク値の２．０倍以下
×：樹脂のみのトルク値の３．０倍以下
（分散性評価）
複合樹脂を３０ｍｇ計量し、スライドガラスにのせ、２４０℃のホットスターラー（商品名：ＲＥＸＩＭ、型番：ＲＳＨ−６ＤＮ、株式会社アズワン製）で加熱する。樹脂が溶融したところで、もう一枚のスライドガラスをかぶせてプレスし、冷却することで分散評価用サンプルが得られる。
分散性評価には微分干渉装置と位相差装置を備えた生物顕微鏡（商品名：エクリプス、型番：Ｎｉ−Ｕ、株式会社ニコン製）を用いた。倍率２００倍でランダムに１０視野を観察し、１０μｍ以上の粗大物をカウントし、１０視野の合計数をもとに以下の基準で〇以上を合格とした。
◎：粗大物がない。
〇：粗大物が１０個未満。
△：粗大物が１０〜１００個
×：粗大物が１００個以上
（多孔質体の密度測定）
多孔質体を１０ｃｍ四方に裁断し、重さは電子天秤（型番：ＦＺ−３０００ｉＷｐ、メトラー・トレド株式会社製）を用い、厚さはシックネスゲージ（型番：５４７−４０１、株式会社ミツトヨ製）で１０点測定し、その平均値を算出した。この重さと厚さから密度を算出した。
（粉体の嵩密度測定）
ＪＩＳ Ｋ７３６５に従って測定した。
[Measurement items and test methods in the examples]
(Kneading test)
A kneading machine (trade name: Labplast mill, model: 4C-150, manufactured by Toyo Seiki Co., Ltd.) and a mixer (model number: R60, manufactured by Toyo Seiki Co., Ltd.) were used for the kneading test. 41 g of polypropylene resin (model number: J105G, manufactured by Prime Polymer Co., Ltd.) was weighed, put into a mixer heated to 220 ° C., and pre-kneaded at 10 rpm. Then, the rotation speed was changed to 30 rpm, 1 g of the fine cellulose fiber powder was weighed and charged, and after the charging was completed, the rotation speed was changed to 50 rpm and kneaded for 10 minutes. The torque value at the end of kneading was read, and 〇 or higher was passed according to the following criteria.
⊚: 1.2 times or less of the torque value of resin only 〇: 1.5 times or less of the torque value of resin only △: 2.0 times or less of the torque value of resin only ×: 3.0 of the torque value of resin only Less than double
(Dispersity evaluation)
Weigh 30 mg of the composite resin, place it on a slide glass, and heat it with a hot stirrer (trade name: REXIM, model number: RSH-6DN, manufactured by AS ONE Corporation) at 240 ° C. When the resin is melted, it is covered with another slide glass, pressed, and cooled to obtain a sample for dispersion evaluation.
A biological microscope (trade name: Eclipse, model number: Ni-U, manufactured by Nikon Corporation) equipped with a differential interference contrast device and a phase contrast device was used for the dispersion evaluation. 10 visual fields were randomly observed at a magnification of 200 times, and coarse objects of 10 μm or more were counted, and based on the total number of 10 visual fields, 〇 or more was passed according to the following criteria.
⊚: There are no oversized items.
〇: Less than 10 oversized items.
Δ: 10 to 100 oversized items ×: 100 or more oversized items
(Measurement of density of porous material)
The porous body is cut into 10 cm squares, the weight is an electronic balance (model number: FZ-3000iWp, manufactured by METTLER TOLEDO Co., Ltd.), and the thickness is a thickness gauge (model number: 547-401, manufactured by Mitutoyo Co., Ltd.). 10 points were measured and the average value was calculated. The density was calculated from this weight and thickness.
(Measurement of bulk density of powder)
Measured according to JIS K7365.
（実施例１）
［微細セルロース繊維の調成工程］
針葉樹晒クラフトパルプをイオン交換水中に２重量％濃度になるように分散させ、ダブルディスクリファイナーを用いて叩解し、さらに高圧ホモジナイザー（エスエムテー株式会社製、ＬＡＢ１０００）を用いて７５０ｂａｒの圧力に調整して１０回処理することにより微細セルロース繊維を得た。
(Example 1)
[Preparation process of fine cellulose fibers]
Disperse softwood bleached kraft pulp in ion-exchanged water to a concentration of 2% by weight, beat it with a double discifier, and adjust the pressure to 750 bar using a high-pressure homogenizer (LAB1000, manufactured by SMT Co., Ltd.). Fine cellulose fibers were obtained by treating 10 times.
[微細セルロース繊維の濃縮工程]
上記調成工程で得られた微細セルロース繊維を４２０メッシュのポリエステル製メッシュ（型番：Ｔ−No.４２０Ｔ、ＮＢＣメッシュテック社製）と吸水紙で挟み、プレス脱水して固形分濃度１５％の微細セルロース繊維ペーストに調整した。
[Concentration process of fine cellulose fibers]
The fine cellulose fibers obtained in the above preparation step are sandwiched between 420 mesh polyester mesh (model number: T-No.420T, manufactured by NBC Meshtec Inc.) and water-absorbent paper, press-dehydrated, and have a solid content concentration of 15%. Adjusted to cellulose fiber paste.
［混合ペースト調成工程］
上記濃縮工程得られた微細セルロース繊維ペーストに微細セルロース繊維の固形分濃度が５．５％、ｔ−ブチルアルコールの濃度が２０％になるよう、ｔ−ブチルアルコールとイオン交換水を加え、プラネタリーミキサー（型番：ＰＶＭ−５、淺田鉄工株式会社製）を用い、均一になるまで混錬し、混合ペーストを得た。
[Mixed paste preparation process]
To the fine cellulose fiber paste obtained in the above concentration step, t-butyl alcohol and ion-exchanged water are added so that the solid content concentration of the fine cellulose fibers is 5.5% and the concentration of t-butyl alcohol is 20%. Using a mixer (model number: PVM-5, manufactured by Asada Iron Works Co., Ltd.), kneading was performed until uniform to obtain a mixed paste.
［凍結乾燥工程］
凍結乾燥には真空凍結乾燥装置（型番：ＳＦ−４ＫＢ、三庄インダストリー株式会社製）を用いた。得られた混合ペーストをステンレス製のバットに敷き詰め、−３５℃で６時間の予備凍結し、その後、０．１ｋＰａ以下になるよう真空度を調整しながら段階的に昇温することで微細セルロース繊維の多孔質体が得られた。
[Freeze-drying process]
A vacuum freeze-dryer (model number: SF-4KB, manufactured by Sansho Industry Co., Ltd.) was used for freeze-drying. The obtained mixed paste was spread on a stainless steel vat, pre-frozen at −35 ° C. for 6 hours, and then gradually heated to 0.1 kPa or less while adjusting the degree of vacuum to obtain fine cellulose fibers. The porous body of was obtained.
［粉砕工程］
上記多孔質体をホモミキサー（型番：ＣＭ−１００、株式会社アズワン製）で予備粉砕後、気流式粉砕機（商品名：ドライバースト、型番：ＤＢ−１００Ｓ、株式会社スギノマシン製）を用い、回転数１８，０００ｒｅｖ／ｍｉｎで粉砕し、粉末状微細セルロース繊維が得られた。
[Crushing process]
After pre-grinding the porous body with a homomixer (model number: CM-100, manufactured by AS ONE Co., Ltd.), use an airflow crusher (trade name: Dryst, model number: DB-100S, manufactured by Sugino Machine Limited). Milling was performed at a rotation speed of 18,000 rev / min to obtain powdered fine cellulose fibers.
[化学修飾工程１]
２００ｍｌビーカーにアセトン１００ｍｌと０．７５ｇのトリメトキフェニルシシラン（東京化成工業株式会社製）を入れてマグネチックスターラーで撹拌後、上記微細セルロース繊維粉末１．５ｇを加えて、２時間撹拌する。その後、ＰＴＦＥタイプのメンブランフィルター（商品名：オムニポア、径：１．０μｍ、メルクミリポア社製）を備えたろ過器でろ過し、残渣を１２０℃で２時間乾燥することで化学修飾した粉末状微細セルロース繊維Ｅ１が得られた。
[Chemical modification step 1]
100 ml of acetone and 0.75 g of trimetokiphenylsilan (manufactured by Tokyo Kasei Kogyo Co., Ltd.) are placed in a 200 ml beaker and stirred with a magnetic stirrer, then 1.5 g of the above fine cellulose fiber powder is added and the mixture is stirred for 2 hours. Then, it is filtered with a filter equipped with a PTFE type membrane filter (trade name: Omnipore, diameter: 1.0 μm, manufactured by Merck Millipore), and the residue is chemically modified by drying at 120 ° C. for 2 hours. Cellulose fiber E1 was obtained.
（実施例２）
[化学修飾工程２]
２．５Ｌのステンレス製密閉容器に、２．５ｇのフェニルトリメトキシシランを入れた５０ｍｌビーカーを入れ、隙間に上記微細セルロース繊維粉末を敷き詰める。１２０℃のオーブンに入れて２時間反応させることで化学修飾した粉末状微細セルロース繊維Ｅ２が得られた。
(Example 2)
[Chemical modification step 2]
A 50 ml beaker containing 2.5 g of phenyltrimethoxysilane is placed in a 2.5 L stainless steel airtight container, and the fine cellulose fiber powder is spread in the gaps. The powdery fine cellulose fiber E2 chemically modified was obtained by putting it in an oven at 120 ° C. and reacting it for 2 hours.
(実施例３)
[化学修飾工程３]
２００ｍｌビーカーにアセトン１００ｍｌと０．７５ｇのフェニルイソシアネート（東京化成工業株式会社製）を入れてマグネチックスターラーで撹拌後、上記微細セルロース繊維粉末１．５ｇを加えて、２時間撹拌する。その後、ＰＴＦＥ製のメンブランフィルター（商品名：オムニポア、径：１．０μｍ、メルクミリポア社製）を備えたろ過器でろ過し、さらにシクロヘキサンで１回、アセトンで１回、ろ過洗浄を繰り返したのち、残渣を１０５℃で４時間乾燥することで化学修飾微細セルロース繊維粉末Ｅ３が得られた。
(Example 3)
[Chemical modification step 3]
Put 100 ml of acetone and 0.75 g of phenyl isocyanate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in a 200 ml beaker and stir with a magnetic stirrer, then add 1.5 g of the fine cellulose fiber powder and stir for 2 hours. After that, it is filtered with a filter equipped with a PTFE membrane filter (trade name: Omnipore, diameter: 1.0 μm, manufactured by Merck Millipore), and further filtered and washed once with cyclohexane and once with acetone. The residue was dried at 105 ° C. for 4 hours to obtain a chemically modified fine cellulose fiber powder E3.
（実施例４）
[化学修飾工程４]
混合ペースト調成工程において微細セルロース繊維１００重量部に対し、フェニルトリメトキシシラン５０重量部を配合して実施例１と同様の手法で凍結乾燥を実施した。得られた多孔質体を１２０℃のオーブンで２時間処理し、実施例１と同様の手法で粉砕工程を行った。得られた粉末をＰＴＦＥ製のメンブランフィルター（商品名：オムニポア、径：１．０μｍ、メルクミリポア社製）を備えたろ過器を用い、シクロヘキサンで１回、アセトンで１回、ろ過洗浄したのち、残渣を１０５℃で４時間乾燥することで化学修飾した粉末状微細セルロース繊維Ｅ４が得られた。
(Example 4)
[Chemical modification step 4]
In the mixed paste preparation step, 50 parts by weight of phenyltrimethoxysilane was added to 100 parts by weight of the fine cellulose fibers, and freeze-drying was carried out in the same manner as in Example 1. The obtained porous body was treated in an oven at 120 ° C. for 2 hours, and a pulverization step was carried out in the same manner as in Example 1. The obtained powder is filtered and washed once with cyclohexane and once with acetone using a filter equipped with a membrane filter made of PTFE (trade name: Omnipore, diameter: 1.0 μm, manufactured by Merck Millipore). The residue was dried at 105 ° C. for 4 hours to obtain chemically modified fine powdery cellulose fiber E4.
（実施例５）
混合ペーストの調成工程において、微細セルロース繊維の固形分濃度を８．５％とする以外は実施例１と同様の手法で化学修飾した微細セルロース繊維Ｅ５が得られた。
(Example 5)
In the step of preparing the mixed paste, the fine cellulose fiber E5 chemically modified by the same method as in Example 1 except that the solid content concentration of the fine cellulose fiber was set to 8.5% was obtained.
(比較例１)
混合ペーストの調成工程において、微細セルロース繊維の固形分濃度を４．５％とする以外は実施例１と同様の手法で化学修飾した粉末状微細セルロース繊維ＣＥ１が得られた。
(Comparative Example 1)
In the step of preparing the mixed paste, powdered fine cellulose fiber CE1 chemically modified by the same method as in Example 1 except that the solid content concentration of the fine cellulose fiber was set to 4.5% was obtained.
(比較例２)
混合ペーストの調成工程において、微細セルロース繊維の固形分濃度を９．５％とする以外は実施例１と同様の手法で化学修飾した粉末状微細セルロース繊維ＣＥ２が得られた。
(Comparative Example 2)
In the step of preparing the mixed paste, the powdery fine cellulose fiber CE2 chemically modified by the same method as in Example 1 except that the solid content concentration of the fine cellulose fiber was set to 9.5% was obtained.
(比較例３)
混合ペーストの調成工程において、微細セルロース繊維の固形分濃度を１．０％とする以外は実施例１と同様の手法で化学修飾した粉末状微細セルロース繊維ＣＥ３が得られた。
(Comparative Example 3)
In the step of preparing the mixed paste, the powdery fine cellulose fiber CE3 chemically modified by the same method as in Example 1 except that the solid content concentration of the fine cellulose fiber was set to 1.0% was obtained.
(比較例４)
粉砕工程において、５０ｍｌのステンレス製粉砕ジャーと２５ｍｍ径のステンレス製ボールを備えた粉砕機（商品名：ミキサーミル、型番：ＭＭ４００、株式会社レッチェ製）を用い、２５Ｈｚで３分処理する以外は実施例１と同様の手法で化学修飾微細セルロース繊維ＣＥ４が得られた。
(Comparative Example 4)
In the crushing process, a crusher equipped with a 50 ml stainless steel crusher and a 25 mm diameter stainless steel ball (trade name: mixer mill, model number: MM400, manufactured by Lecce Co., Ltd.) is used, except for processing at 25 Hz for 3 minutes. Chemically modified fine cellulose fiber CE4 was obtained in the same manner as in Example 1.
（比較例５）
混合ペースト調成工程において微細セルロース繊維１００重量部に対し、分散剤（商品名：アロンＡ−６１１４、東亜合成株式会社製）を１０重量部添加し、後工程の化学修飾工程を行わないこと以外は実施例１と同様の手法で粉末状微細セルロース繊維ＣＥ５が得られた。
(Comparative Example 5)
Except for adding 10 parts by weight of a dispersant (trade name: Aron A-6114, manufactured by Toa Synthetic Co., Ltd.) to 100 parts by weight of fine cellulose fibers in the mixed paste preparation step and not performing the chemical modification step in the subsequent step. The powdery fine cellulose fiber CE5 was obtained in the same manner as in Example 1.
［表１］
実施例１〜５の結果から、本発明の粉末状微細セルロース繊維が樹脂との複合化において、分散性が良好でありながらも効率よく成形できることが分かる。一方で、比較例の結果より、嵩密度が本発明の範囲外では分散性または成形性に不具合があることが分かる。 From the results of Examples 1 to 5, it can be seen that the powdered fine cellulose fibers of the present invention can be efficiently molded while having good dispersibility in the composite with the resin. On the other hand, from the results of the comparative examples, it can be seen that there is a problem in dispersibility or moldability when the bulk density is outside the range of the present invention.
Claims (13)
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